Dithienobenzofuran polymers and small molecules for electronic application

ABSTRACT

The present invention relates to polymers comprising a repeating unit of the formula (I), and compounds of formula (VIII), or (IX), wherein Y, Y 15 , Y 16  and Y 17  are independently of each other a group of formula (I), and their use as organic semiconductor in organic electronic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

The present invention relates to polymers comprising a repeating unit of the formula (I) and compounds of formula (VIII), or (IX), wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group of formula (I), and their use as organic semiconductor in organic electronic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

WO2010136401 relates to polycyclic dithiophenes of the following formula

wherein

R¹ and R^(1′) independently of each other are H or a substituent, halogen or SiR⁶R⁴R⁵;

R² and R^(2′) may be the same or different and are selected from C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, C₄-C₂₅aryl, C₅-C₂₅alkylaryl or C₅-C₂₅aralkyl, each of which is unsubstituted or substituted, and if R³ and R^(3′) within the definition of X together complete a ring structure, or X is a bridging group conforming to one of the formulae

R² and/or R^(2′) may also be halogen or hydrogen;

X is a divalent linking group selected from

Y and Y′ independently are selected from

n and p independently range from 0 to 6;

R³ and R^(3′) independently are hydrogen or a substituent, or are amino, or together, with the carbon atoms they are attached to, complete a 5- or 6-membered unsubstituted or substituted hydrocarbon ring, or a 5-membered unsubstituted or substituted heterocyclic ring comprising at least one hetero atom selected from N, O, or S; as well as oligomers, polymers or copolymers comprising at least 2 structural units of the formula

The substances described in WO2010136401 are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

WO2011002927 relates to is directed to a (copolymer) composition comprising at least one donor acceptor copolymer, said at least one copolymer comprising at least one first bithiophene repeat unit (donor) represented by formula

wherein R₁, R₂ and R′ are solubilizing groups or hydrogen. According to claim 8 of WO2011002927 R¹ and R² may form a heterocyclic ring.

In addition, polymers comprising a bithiophene repeating unit are described in EP2006291A1, US20110006287 and WO2011025454.

PCT/EP2013/056463 relates to organic electronic devices comprising polymers or small molecules comprising at least one (repeating) unit of the formulas (I) and (II)

Schroeder B. C. et al., Chem. Mater., 23 (2011) 4025-4031 describe the use of polymers comprising monomers units of formula M1 and M2 in manic field effect transistors:

James R. Durrant et al., J. Phys. Chem. Lett. 2012, 3, 140-144 report on the contribution of photoinduced hole transfer to the device photocurrent for an OPV device with an active layer comprising a blend film of the small bandgap polymer

It is one object of the present invention to provide polymers, which show high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability, when used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

Said object has been solved by polymers, comprising a repeating unit of the formula

wherein

R¹ and R² are independently of each other H, F, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E′ and/or interrupted by D′, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G′, or

R¹ and R² form together a group

wherein

R²⁰⁵, R²⁰⁶, R^(206′), R²⁰⁷, R²⁰⁸, R^(208′), R²⁰⁹ and R²¹⁰ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E′ and/or interrupted by D′, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is substituted by E′ and/or interrupted by D′, C₁-C₁₈fluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G′, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl which is substituted by G′; CN, or —CO—R²⁸,

R⁶⁰¹ and R⁶⁰² are independently of each other H, halogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G′, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl which is substituted by G′;

D′ is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR⁶⁵—, —SiR⁷⁰R⁷¹—, —POR⁷²—, —CR⁶³═CR⁶⁴—, or —C≡C—, and

E′ is —OR⁶⁹, —SR⁶⁹, —NR⁶⁵R⁶⁶, —COR⁶⁸, —COOR⁶⁷, —CONR⁶⁵R⁶⁶, —CN, CF₃, or halogen,

G′ is E′, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—,

R²⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁶³ and R⁶⁴ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;

R⁶⁵ and R⁶⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; or

R⁶⁵ and R⁶⁶ together form a five or six membered ring,

R⁶⁷ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁶⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁶⁹ is C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁷⁰ and R⁷¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and

R⁷² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl.

Advantageously, the polymer of the present invention, or an organic semiconductor material, layer or component, comprising the polymer of the present invention, can be used in organic light emitting diodes (PLEDs, OLEDs), organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).

The polymers of this invention preferably have a weight average molecular weight of 4,000 Daltons or greater, especially 4,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000 and most preferably 10,000 to 100,000 Daltons. Molecular weights are determined according to high-temperature gel permeation chromatography (HT-GPC) using polystyrene standards. The polymers of this invention preferably have a polydispersity of 1.01 to 10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5. The polymers of the present invention are preferably conjugated.

Oligomers of the present invention preferably have a weight average molecular weight below 4,000 Daltons.

In a preferred embodiment R¹ and R² form together a group

R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are preferably H.

In another preferred embodiment R¹ and R² are a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are independently of each other H, CN, F, CF³, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—. R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are preferably H.

R¹ and R² may be different, but are preferably the same.

In a preferred embodiment the present invention is directed to polymers comprising a repeating unit of the formula

wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of each other H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, or R¹ and R² form together a group

R⁶⁰¹ and R⁶⁰² may be the same or different and are selected from C₁-C₂₅alkyl, or hydrogen; especially hydrogen. R¹ and R² are especially a group of formula

very especially

Among the repeating units of formula I repeating units of formula

(Ia) are preferred.

The polymer may be a homopolymer of formula

wherein A is a repeating unit of formula (I), n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.

Alternatively, the polymer may be a polymer, comprising repeating units of the formula

especially

very especially a copolymer of formula

wherein

n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.

A is a repeating unit of formula (I), and

—COM¹- is a repeating unit

wherein

k is 0, 1, 2, or 3; l is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3;

Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other a group of formula and

such as, for example,

such as, for example,

wherein

X¹ is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—, —C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

such as, for example,

such as, for example,

wherein

X^(1′) is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—, —C(R¹⁰⁶)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are independently of each other hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano, COOR¹⁰³, a C₁-C₂₅alkyl group, or C₆-C₂₄aryl or C₂-C₂₀heteroaryl,

R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) are independently of each other hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;

R⁷, R^(7′), R⁹ and R^(9′) are independently of each other hydrogen, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C₇-C₂₅arylalkyl,

R⁸ and R^(8′) are independently of each other hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,

R¹¹ and R^(11′) are independently of each other C₁-C₂₅alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy;

R¹² and R^(12′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; or

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, C₁-C₁₈alkyl, C₆-C₁₀aryl, which may optionally be substituted by G, or C₂-C₈heteroaryl, which may optionally be substituted by G,

R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₁₈alkoxy,

R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl; C₁-C₂₅alkyl; which may be interrupted by —O—, or —S—; or —COOR¹⁰³;

R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E and/or interrupted by D, C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or

R¹⁰⁸ and R¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, wherein

R¹¹⁰ and R¹¹¹ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or

R¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, which optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl,

D is —CO—, —COO—, —S—, —O—, or —NR^(112′)—,

E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR^(112′)R^(113′), —CONR^(112′)R^(113′), or halogen,

G is E, or C₁-C₁₈alkyl, and

R^(112′) and R^(113′) are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group;

R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group, C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one to three times with C₁-C₈alkyl and/or C₁-C₈alkoxy;

R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are independently of each other hydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;

R¹²² and R^(122′) are independently of each other hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl.

R²⁰¹ is selected from hydrogen, a C₁-C₁₀₀alkyl group, —COOR¹⁰³, a C₁-C₁₀₀alkyl group substituted by one or more halogen atoms, hydroxyl groups, nitro groups, —CN, or C₆-C₁₈aryl groups and/or interrupted by —O—, —COO—, —OCO— or —S—; a C₇-C₂₅arylalkyl group, a carbamoyl group, a C₅-C₁₂cycloalkyl group, which can be substituted one to three times with C₁-C₁₀₀alkyl and/or C₁-C₁₀₀alkoxy, a C₆-C₂₄aryl group, in particular phenyl or 1- or 2 naphtyl which can be substituted one to three times with C₁-C₁₀₀alkyl, C₁-C₁₀₀thioalkoxy, and/or C₁-C₁₀₀alkoxy; and pentafluorophenyl;

R¹⁰³ and R¹¹⁴ are independently of each other C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms,

R²⁰² and R²⁰³ may be the same or different and are selected from H, F, —CN, C₁-C₁₀₀alkyl, which may optionally be interrupted by one or more oxygen, or sulphur atoms; and C₁-C₁₀₀alkoxy.

The above-mentioned repeating units COM¹ are known and can be prepared according to known procedures. With respect to DPP repeating units and their synthesis reference is, for example, made to U.S. Pat. No. 6,451,459B1, WO05/049695, WO2008/000664, EP2034537A2, EP2075274A1, WO2010/049321, WO2010/049323, WO2010/108873, WO2010/115767, WO2010/136353, WO2010/136352 and PCT/EP2011/057878.

R³, R^(3′), R⁴ and R^(4′) are preferably hydrogen, or C₁-C₂₅alkyl.

R²⁰¹ is preferably a linear, or branched C₁-C₃₆alkyl group, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, especially n-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-ethyl-hexyl, 2-butyl-hexyl, 2-butyl-octyl, 2-hexyldecyl, 2-decyl-tetradecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, or tetracosyl.

Advantageously, the groups R²⁰¹ can be represented by formula

wherein m1=n1+2 and m1+n1≦24. Chiral side chains can either be homochiral, or racemic, which can influence the morphology of the compounds.

—COM¹- preferably a repeating unit of formula

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each other hydrogen, or C₁-C₂₅alkyl;

R⁸ and R^(8′) are independently of each other hydrogen, or C₁-C₂₅alkyl;

R¹¹⁴ is a C₁-C₃₈alkyl group;

R²⁰¹ is a C₁-C₃₈alkyl group; and

R²⁰² and R^(203′) are independently of each other hydrogen or C₁-C₂₅alkyl.

In a particularly preferred embodiment COM¹ is selected from repeating units of formula (XVb), (XVb′), (XVe), (XVh), (XVh′), (XVu′), (XVu″), and (XVu′″), especially (XVb), (XVb′), (XVu′), (XVu″), and (XVu′″).

In a preferred embodiment of the present invention the polymer is a copolymer, comprising repeating units of formula

especially a copolymer of formula

wherein A and COM¹ are as defined above; n is a number which results in a molecular weight of 4,000 to 2,000,000 Daltons, more preferably 10,000 to 1,000,000 and most preferably 10,000 to 100,000 Daltons. n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150. The polymer structure represented by formula III is an idealized representation of the polymer products obtained, for example, via the Suzuki polymerization procedure. The repeating unit of formula

can be incorporated into the polymer chain in two ways:

Both possibilities shall be covered by formula (III).

The polymers of the present invention can comprise more than 2 different repeating units, such as, for example, repeating units A, COM¹ and B, which are different from each other. In said embodiment the polymer is a copolymer, comprising repeating units of formula

wherein x=0.995 to 0.005, y=0.005 to 0.995, especially x=0.2 to 0.8, y=0.8 to 0.2, and x+y=1. B has the meaning of COM¹, with the proviso that B is different from COM¹. A and COM¹ are as defined above.

In another preferred embodiment of the present invention A is a repeating unit of formula (I), especially (Ia), as defined above, and

is a group of formula

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each other hydrogen or C₁-C₂₅alkyl;

R⁸ and R^(8′) are independently of each other hydrogen or C₁-C₂₅alkyl; and

R²⁰¹ is a C₁-C₃₈alkyl group.

COM¹ is preferably a repeating unit of formula (XVb′), (XVb′), (XVu′) and (XVu″).

Among the repeating units of formula (I) repeating units of formula (I) are preferred, wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of each other H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, or R¹ and R² form together a group

R¹ and R² are especially a group of formula

very especially a group of formula

R¹ and R² may be the different, but are preferably the same. R⁶⁰¹ and R⁶⁰² may be the different, but are preferably the same and are selected from hydrogen, or C₁-C₂₅alkyl, especially hydrogen. Most preferred are repeating units of formula (Ia).

Among the copolymers of formula III the following copolymers are preferred:

wherein

n is 4 to 1000, especially 4 to 200, very especially 5 to 150;

R³, R^(3′), R⁴ and R^(4′) are independently of each other hydrogen or C₁-C₂₅alkyl;

R²⁰¹ is a C₁-C₃₈alkyl group, and

R⁶⁰¹ and R⁶⁰² are independently of each other hydrogen, or C₁-C₂₅alkyl; especially hydrogen. Polymers of formula (Ia1), (Ia2), (Ia6) and (Ia7) are more preferred.

Examples of particularly preferred polymers are shown below:

Copolymers of formula III can be obtained, for example, by the Suzuki reaction. The condensation reaction of an aromatic boronate and a halogenide, especially a bromide, commonly referred to as the “Suzuki reaction”, is tolerant of the presence of a variety of organic functional groups as reported by N. Miyaura and A. Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 (1995). Preferred catalysts are 2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(II)acetates, tri-alykl-phosphonium salts/palladium (0) derivatives and tri-alkylphosphine/palladium (0) derivatives. Especially preferred catalysts are 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl (sPhos)/palladium(II)acetate and, tri-tert-butylphosphonium tetrafluoroborate ((t-Bu)₃P*HBF₄)/tris(dibenzylideneacetone)dipalladium (0) (Pd₂(dba)₃) and tri-tert-butylphosphine (t-Bu)₃P/tris(dibenzylideneacetone)dipalladium (0) (Pd₂(dba)₃). This reaction can be applied to preparing high molecular weight polymers and copolymers.

To prepare polymers corresponding to formula III a dihalogenide of formula X¹⁰-A-X¹⁰ is reacted with an (equimolar) amount of a diboronic acid or diboronate corresponding to formula

or a dihalogenide of formula

is reacted with an (equimolar) amount of a diboronic acid or diboronate corresponding to formula X¹¹-A-X¹¹, wherein X¹⁰ is halogen, especially Br, and X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group and Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹C¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or a C₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or —C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkyl group, under the catalytic action of Pd and triphenylphosphine. The reaction is typically conducted at about 0° C. to 180° C. in an aromatic hydrocarbon solvent such as toluene, xylene. Other solvents such as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon. An aqueous base, preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scavenger. A polymerization reaction may take 0.2 to 100 hours. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Control of molecular weight is possible by using either an excess of dibromide, diboronic acid, or diboronate, or a chain terminator.

According to the process described in WO2010/136352 the polymerisation is carried out in presence of

a) a catalyst/ligand system comprising a palladium catalyst and an organic phosphine or phosphonium compound,

b) a base,

c) a solvent or a mixture of solvents, characterized in that

the organic phosphine is a trisubstituted phosphine of formula

or phosphonium salt thereof, wherein X″ independently of Y″ represents a nitrogen atom or a C—R^(2″) group and Y″ independently of X″ represents a nitrogen atom or a C—R^(9″) group, R^(1″) for each of the two R^(1″) groups independently of the other represents a radical selected from the group C₁-C₂₄-alkyl, C₃-C₂₀-cycloalkyl, which includes especially both monocyclic and also bi- and tri-cyclic cycloalkyl radicals, C₅-C₁₄-aryl, which includes especially the phenyl, naphthyl, fluorenyl radical, C₂-C₁₃-heteroaryl, wherein the number of hetero atoms, selected from the group N, O, S, may be from 1 to 2, wherein the two radicals R^(1″) may also be linked to one another,

and wherein the above-mentioned radicals R¹″ may themselves each be mono- or poly-substituted independently of one another by substituents selected from the group hydrogen, C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₃-C₈-cycloalkyl, C₂-C₉-hetero-alkyl, C₅-C₁₀-aryl, C₂-C₉-heteroaryl, wherein the number of hetero atoms from the group N, O, S may be from 1 to 4, C₁-C₂₀-alkoxy, C₁-C₁₀-haloalkyl, hydroxy, amino of the forms NH—(C₁-C₂₀-alkyl), NH—(C₅-C₁₀-aryl), N(C₁-C₂₀-alkyl)₂, N(C₁-C₂₀-alkyl)(C₅-C₁₀-aryl), N(C₅-C₁₀-aryl)₂, N(C₁-C₂₀-alkyl/C₅-C₁₀-aryl₃)₃ ₊ , NH—CO—C₁-C₂₀-alkyl, NH—CO—C₅-C₁₀-aryl, carboxylato of the forms COOH and COOQ (wherein Q represents either a monovalent cation or C₁-C₈-alkyl), C₁-C₆-acyloxy, sulfinato, sulfonato of the forms SO₃H and SO₃Q′ (wherein Q′ represents either a monovalent cation, C₁-C₂₀-alkyl, or C₅-C₁₀-aryl), tri-C₁-C₆-alkylsilyl, wherein two of the mentioned substituents may also be bridged with one another, R^(2″)-R^(9″) represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl, N-(alkyl)₂, O-(aryl), NH-(aryl), N-(alkyl)(aryl), O—CO-alkyl, O—CO-aryl, F, Si(alkyl)₃, CF₃, CN, CO₂H, COH, SO₃H, CONH₂, CONH(alkyl), CON(alkyl)₂, SO₂(alkyl), SO(alkyl), SO(aryl), SO₂(aryl), SO₃(alkyl), SO₃(aryl), S-alkyl, S-aryl, NH—CO(alkyl), CO₂(alkyl), CONH₂, CO(alkyl), NHCOH, NHCO₂(alkyl), CO(aryl), CO₂(aryl) radical, wherein two or more adjacent radicals, each independently of the other (s), may also be linked to one another so that a condensed ring system is present and wherein in R^(2″) to R^(9″) alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms which may in each case be linear or branched, alkenyl represents a mono- or poly-unsaturated hydrocarbon radical having from 2 to 20 carbon atoms which may in each case be linear or branched, cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms, aryl represents a 5- to 14-membered aromatic radical, wherein from one to four carbon atoms in the aryl radical may also be replaced by hetero atoms from the group nitrogen, oxygen and sulfur so that a 5- to 14-membered heteroaromatic radical is present, wherein the radicals R^(2″) to R^(9″) may also carry further substituents as defined for R^(1″).

The organic phosphines and their synthesis are described in WO2004101581.

Preferred organic phosphines are selected from trisubstituted phosphines of formula

Cpd. R^(1″) R^(5″) R^(6″) R^(3″) R^(4″) A-1 

H H H H A-2  cyclohexyl H H H H A-3  phenyl H H H H A-4  adamantyl H H H H A-5  cyclohexyl —OCH₃ H H H A-6  cyclohexyl ¹⁾ ¹⁾ H H A-7 

¹⁾ ¹⁾ H H A-8  phenyl ¹⁾ ¹⁾ H H A-9  adamantyl ¹⁾ ¹⁾ H H A-10 cyclohexyl H H ²⁾ ²⁾ A-11

H H ²⁾ ²⁾ A-12 phenyl H H ²⁾ ²⁾ A-13 adamantyl H H ²⁾ ²⁾

Examples of preferred catalysts include the following compounds:

palladium(II) acetylacetonate, palladium(0) dibenzylidene-acetone complexes, palladium(II) propionate,

Pd₂(dba)₃: [tris(dibenzylideneacetone)dipalladium(0)],

Pd(dba)₂: [bis(dibenzylideneacetone) palladium(0)],

Pd(PR₃)₂, wherein PR₃ is a trisubstituted phosphine of formula VI,

Pd(OAc)₂: [palladium(II) acetate], palladium(II) chloride, palladium(II) bromide, lithium tetrachloropalladate(II),

PdCl₂(PR₃)₂; wherein PR₃ is a trisubstituted phosphine of formula VI; palladium(0) diallyl ether complexes, palladium(II) nitrate,

PdCl₂(PhCN)₂: [dichlorobis(benzonitrile) palladium(II)],

PdCl₂(CH₃CN): [dichlorobis(acetonitrile) palladium(II)], and

PdCl₂(COD): [dichloro(1,5-cyclooctadiene) palladium(II)].

Especially preferred are PdCl₂, Pd₂(dba)₃, Pd(dba)₂, Pd(OAc)₂, or Pd(PR₃)₂. Most preferred are Pd₂(dba)₃ and Pd(OAc)₂.

The palladium catalyst is present in the reaction mixture in catalytic amounts. The term “catalytic amount” refers to an amount that is clearly below one equivalent of the (hetero)aromatic compound(s), preferably 0.001 to 5 mol-%, most preferably 0.001 to 1 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used.

The amount of phosphines or phosphonium salts in the reaction mixture is preferably from 0.001 to 10 mol-%, most preferably 0.01 to 5 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The preferred ratio of Pd:phosphine is 1:4.

The base can be selected from all aqueous and nonaqueous bases and can be inorganic, or organic. It is preferable that at least 1.5 equivalents of said base per functional boron group is present in the reaction mixture. Suitable bases are, for example, alkali and alkaline earth metal hydroxides, carboxylates, carbonates, fluorides and phosphates such as sodium and potassium hydroxide, acetate, carbonate, fluoride and phosphate or also metal alcoholates. It is also possible to use a mixture of bases. The base is preferably a lithium salt, such as, for example, lithium alkoxides (such as, for example, lithium methoxide and lithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluoride and/or phosphate.

The at present most preferred base is aqueous LiOHxH₂O (monohydrate of LiOH) and (waterfree) LiOH.

The reaction is typically conducted at about 0° C. to 180° C., preferably from 20 to 160° C., more preferably from 40 to 140° C. and most preferably from 40 to 120° C. A polymerization reaction may take 0.1, especially 0.2 to 100 hours.

In a preferred embodiment of the present invention the solvent is tetrahydrofuran (THF), the base is LiOH*H2O and the reaction is conducted at reflux temperature of THF (about 65° C.).

The solvent is for example selected from toluene, xylenes, anisole, THF, 2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene or solvent mixtures comprising one or more solvents like e.g. THF/toluene and optionally water. Most preferred is THF, or THF/water.

Advantageously, the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃, (tris(dibenzylideneacetone)dipalladium(0)) and an organic phosphine A-1 to A-13,

b) LiOH, or LiOHxH₂O; and

c) THF, and optionally water. If the monohydrate of LiOH is used, no water needs to be added. The palladium catalyst is present in an amount of preferably about 0.5 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The amount of phosphines or phosphonium salts in the reaction mixture is preferably about 2 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The preferred ratio of Pd:phosphine is about 1:4.

Preferably the polymerization reaction is conducted under inert conditions in the absence of oxygen. Nitrogen and more preferably argon are used as inert gases.

The process described in WO2010/136352 is suitable for large-scale applications, is readily accessible and convert starting materials to the respective polymers in high yield, with high purity and high selectivity. The process can provide polymers having weight average molecular weights of at least 10,000, more preferably at least 20,000, most preferably at least 30,000. The at present most preferred polymers have a weight average molecular weight of 30,000 to 80,000 Daltons. Molecular weights are determined according to high-temperature gel permeation chromatography (HT-GPC) using polystyrene standards. The polymers preferably have a polydispersibility of 1.01 to 10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5.

If desired, a monofunctional aryl halide or aryl boronate, such as, for example,

may be used as a chain-terminator in such reactions, which will result in the formation of a terminal aryl group.

It is possible to control the sequencing of the monomeric units in the resulting copolymer by controlling the order and composition of monomer feeds in the Suzuki reaction.

The polymers of the present invention can also be synthesized by the Stille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004, 14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). To prepare polymers corresponding to formula III a dihalogenide of formula X¹⁰-A-X¹⁰ is reacted with a compound of formula X^(11′)—COM¹-X^(11′), or a dihalogenide of formula X¹⁰—COM¹-X¹⁰ is reacted with a compound of formula X^(11′)-A-X^(11′), wherein X^(11′) is a group —SnR²⁰⁷R²⁰⁸R²⁰⁹ and X¹⁰ is as defined above, in an inert solvent at a temperature in range from 0° C. to 200° C. in the presence of a palladium-containing catalyst, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched. It must be ensured here that the totality of all monomers used has a highly balanced ratio of organotin functions to halogen functions. In addition, it may prove advantageous to remove any excess reactive groups at the end of the reaction by end-capping with monofunctional reagents. In order to carry out the process, the tin compounds and the halogen compounds are preferably introduced into one or more inert organic solvents and stirred at a temperature of from 0 to 200° C., preferably from 30 to 170° C. for a period of from 1 hour to 200 hours, preferably from 5 hours to 150 hours. The crude product can be purified by methods known to the person skilled in the art and appropriate for the respective polymer, for example repeated re-precipitation or even by dialysis.

Suitable organic solvents for the process described are, for example, ethers, for example diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether, hydrocarbons, for example hexane, isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols, for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and tert-butanol, ketones, for example acetone, ethyl methyl ketone and isobutyl methyl ketone, amides, for example dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone, nitriles, for example acetonitrile, propionitrile and butyronitrile, and mixtures thereof.

The palladium and phosphine components should be selected analogously to the description for the Suzuki variant.

Alternatively, the polymers of the present invention can also be synthesized by the Negishi reaction using a zinc reagent A-(ZnX¹²)₂, wherein X¹² is halogen and halides, and COM¹-(X²³)₂, wherein X²³ is halogen or triflate, or using A-(X²³)₂ and COM¹-(ZnX²³)₂. Reference is, for example, made to E. Negishi et al., Heterocycles 18 (1982) 117-22.

Alternatively, the polymers of the present invention can also be synthesized by the Hiyama reaction using a organosilicon reagent A-(SiR²¹⁰R²¹¹R²¹²)₂, wherein R²¹⁰, R²¹¹ and R²¹² are identical or different and are halogen, or C₁-C₆alkyl, and COM¹-(X²³)₂, wherein X²³ is halogen or triflate, or using A-(X²³)₂ and COM¹-(SiR²¹⁰R²¹¹R²¹²)₂. Reference is, for example, made to T. Hiyama et al., Pure Appl. Chem. 66 (1994) 1471-1478 and T. Hiyama et al., Synlett (1991) 845-853.

Homopolymers of the type (A)_(n) can be obtained via Yamamoto coupling of dihalides X¹⁰-A-X¹⁰, where X¹⁰ is halogen, preferably Br. Alternatively homopolymers of the type (A)_(n) can be obtained via oxidative polymerization of units X¹⁰-A-X¹⁰, where X¹⁰ is hydrogen, e.g. with FeCl₃ as oxidizing agent.

A possible synthesis route for monomers useful in the preparation of polymers, comprising repeating units of formula (I), wherein R¹ and R² are the same and are an optionally substituted C₆-C₂₄aryl, or C₂-C₂₀heteroaryl group; is shown below:

Compounds of formula (XVII) can be obtained by reacting compounds of formula (XX) with 1,4-dimethyl-piperazine-2,3-dione in the presence of butyl lithium in an appropriate solvent:

Compounds of formula (XVIII) can be obtained by reacting compounds of formula (XVII) with N-bromosuccinimide (NBS) in an appropriate solvent:

Intermediates for repeating units of formula (I), wherein R¹ and R² form together a group

can be obtained by reacting compounds of formula (XVIII) with cyclohex-2-en-1-one in the presence of TiCl₄ in dichloromethane at elevated temperatures.

Reference is, for example, made to WO2009115413.

The compounds of formula (VIII) and (IX) can be prepared by using the above described intermediates and the synthesis methods described, for example, in WO2012175530 and WO2010/115767.

The compounds of the formula

are intermediates in the production of polymers, are new and form a further subject of the present invention. A^(1′) and A^(2′) are independently of each other a group of formula

wherein X² and X^(2′) are independently of each other halogen, ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and are H or C₁-C₆alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X¹² is a halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group and Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or a C₁-C₁₀alkyl group,

especially —C(CH₃)₂C(CH₃)₂—, —C(CH₃)₂CH₂C(CH₃)₂—, or —CH₂C(CH₃)₂CH₂—; and Y¹³ and Y¹⁴ are independently of each other hydrogen, or a C₁-C₁₀alkyl group. a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴, A⁵ and A^(5′) are as defined above.

The compounds of the formula (IV), or (V) can be used in the production of polymers, comprising repeating unit(s) of formula

wherein

A^(1′) and A^(2′) are independently of each other a group of formula

wherein a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴, A⁵ and A^(5′) are as defined above.

Halogen is fluorine, chlorine, bromine and iodine.

The C₁-C₁₀₀alkyl group is preferably a C₁-C₃₈alkyl group, especially a C₁-C₂₅alkyl group. Reference is made to the definition of R²⁰¹.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl. C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl.

C₂-C₂₅alkenyl (C₂-C₁₈alkenyl) groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₅alkynyl (C₂₋₁₈alkynyl) is straight-chain or branched and preferably C₂₋₈alkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

A halogenated C₁-C₂₅alkyl group is a branched or unbranched radical, wherein all, or part of the hydrogen atoms of the corresponding alkyl group have been replaced by halogen atoms.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthio groups as exemplified further below. The term “aliphatic group” comprises also alkyl groups wherein certain non-adjacent carbon atoms are replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group can be regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

An aliphatic hydrocarbon group having up to 25 carbon atoms is a linear or branched alkyl, alkenyl or alkynyl (also spelled alkinyl) group having up to 25 carbon atoms as exemplified above.

Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) free valencies, e.g. trimethylene or tetramethylene.

Alkenylene is bivalent alkenyl, i.e. alkenyl having two (instead of one) free valencies, e.g. —CH₂—CH═CH—CH₂—.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, be substituted by any acyclic substituents, but are preferably unsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthio groups as exemplified further below. The term “aliphatic group” comprises also alkyl groups wherein certain non-adjacent carbon atoms are replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group can be regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

A cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl group which may be substituted by one or more aliphatic and/or cycloaliphatic hydrocarbon groups.

A cycloaliphatic-aliphatic group is an aliphatic group substituted by a cycloaliphatic group, wherein the terms “cycloaliphatic” and “aliphatic” have the meanings given herein and wherein the free valency extends from the aliphatic moiety. Hence, a cycloaliphatic-aliphatic group is for example a cycloalkyl-alkyl group.

A cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkyl group, e.g. cyclohexyl-methyl.

A “cycloalkenyl group” means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted by one or more aliphatic and/or cycloaliphatic hydrocarbon groups and/or condensed with phenyl groups.

A bivalent group of the formula IVb wherein R²⁸ and R²⁷ together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, is e.g. a group of the formula

wherein A²⁰ represents linear or branched alkylene having up to 25 carbon atoms, preferably ethylene or propylene which may be substituted by one or more alkyl groups, and Y²⁰ represents oxygen or sulphur. For example, the bivalent group of the formula —Y²⁰-A²⁰-O— represents —O—CH₂—CH₂—O— or —O—CH₂—CH₂—CH₂—O—.

A group of the formula IVa wherein two groups R²² to R²⁶ which are in the neighborhood of each other, together represent alkylene or alkenylene having up to 8 carbon atoms, thereby forming a ring, is e.g. a group of the formula

wherein in the group of the formula XXXII R²³ and R²⁴ together represent 1,4-butylene and in the group of the formula XXXIII R²³ and R²⁴ together represent 1,4-but-2-en-ylene.

The C₁-C₁₀₀alkoxy group is preferably a C₁-C₃₈alkoxy group, especially a C₁-C₂₅alkoxy group. C₁-C₂₅alkoxy groups (C₁-C₁₈alkoxy groups) are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of C₁-C₈alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁-C₄alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthio group” means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulfur atom.

C₁-C₁₈fluoroalkyl, especially C₁-C₄fluoroalkyl, is a branched or unbranched radical, wherein all, or part of the hydrogen atoms of the corresponding alkyl group have been replaced by fluorine atoms, such as for example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

The term “carbamoyl group” is typically a C₁₋₁₈carbamoyl radical, preferably C₁₋₈carbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

A cycloalkyl group is typically C₄-C₁₈cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted. The cycloalkyl group, in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with C₁-C₄-alkyl, halogen and cyano. Examples of such condensed cyclohexyl groups are:

in particular

wherein R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵ and R¹⁵⁶ are independently of each other C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particular hydrogen.

C₆-C₂₄aryl (C₆-C₁₈aryl) is typically phenyl, indenyl, azulenyl, naphthyl, biphenyl, as-indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted. Examples of C₆-C₁₂aryl are phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthryl, which may be unsubstituted or substituted.

C₇-C₂₅aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2-phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

Heteroaryl is typically C₂-C₂₀heteroaryl, i.e. a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic group with five to 30 atoms having at least six conjugated m-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted or substituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, a hydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, a cyano group, a carbamoyl group, a nitro group or a silyl group, especially C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen, halo-C₁-C₈alkyl, or a cyano group.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) interrupted by one or more O is, for example, (CH₂CH₂O)₁₋₉—R^(x), where R^(x) is H or C₁-C₁₀alkyl, CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y) is C₁-C₁₈alkyl, and R^(y′) embraces the same definitions as R^(y) or is H.

If a substituent, such as, for example R³, occurs more than one time in a group, it can be different in each occurrence.

The present invention also relates to the use of the polymers, or compounds in an organic, electronic device.

The organic, electronic device is, for example, an organic electroluminescent device (OLED), a polymeric electroluminescent device (PLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field-quench device (O-FQD), a light-emitting electrochemical cell (LEC), or an organic laser diode (O-laser).

For the purposes of the present invention, it is preferred for the polymer, or compound according to the invention to be in the form of a layer (or to be present in a layer) in the electronic device. The polymer, or compound according to the invention can be present in the form of a hole-transport, hole-injection, emitter, electron-transport, electron-injection, charge-blocking and/or charge-generation layer. The polymers, or compounds according to the invention may be, for example, employed as emitting compounds in an emitting layer.

It may additionally be preferred to use the polymer not as the pure substance, but instead as a mixture (blend) together with further polymeric, oligomeric, dendritic or low-molecular-weight substances of any desired type. These may, for example, improve the electronic properties.

A mixture containing a polymer of the present invention results in a semi-conducting layer comprising a polymer of the present invention (typically 5% to 99.9999% by weight, especially 20 to 85% by weight) and at least another material. The other material can be, but is not restricted to a fraction of the same polymer of the present invention with different molecular weight, another polymer of the present invention, a semi-conducting polymer, organic small molecules, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles (Au, Ag etc.), insulator materials like the ones described for the gate dielectric (PET, PS etc.). The polymers of the present invention can be blended with compounds of formula VIII, or IX according to the present invention, or small molecules described, for example, in WO2009/047104, WO2010108873, WO09/047104, U.S. Pat. No. 6,690,029, WO2007082584, and WO2008107089:

WO2007082584:

WO2008107089:

wherein one of Y^(1′) and Y^(2′) denotes —CH═ or ═CH— and the other denotes —X*—,

one of Y^(3′) and Y^(4′) denotes —CH═ or ═CH— and the other denotes —X*—,

X* is —O—, —S—, —Se— or —NR′″—,

R* is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms, or aryl having 2-30 C-atoms, all of which are optionally fluorinated or perfluorinated,

R′ is H, F, Cl, Br, I, CN, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms and optionally being fluorinated or perfluorinated, optionally fluorinated or perfluorinated aryl having 6 to 30 C-atoms, or CO₂R″, with R″ being H, optionally fluorinated alkyl having 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30 C-atoms,

R′″ is H or cyclic, straight-chain or branched alkyl with 1 to 10 C-atoms, y is 0, or 1, x is 0, or 1.

The polymer can contain a small molecule, or a mixture of two, or more small molecule compounds.

Accordingly, the present invention also relates to an organic semiconductor material, layer or component, comprising a polymer according to the present invention.

The polymers of the invention can be used as the semiconductor layer in semiconductor devices. Accordingly, the present invention also relates to semiconductor devices, comprising a polymer of the present invention, or an organic semiconductor material, layer or component. The semiconductor device is especially an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor.

The polymers of the invention can be used alone or in combination as the organic semiconductor layer of the semiconductor device. The layer can be provided by any useful means, such as, for example, vapor deposition (for materials with relatively low molecular weight) and printing techniques. The compounds of the invention may be sufficiently soluble in organic solvents and can be solution deposited and patterned (for example, by spin coating, dip coating, ink jet printing, gravure printing, flexo printing, offset printing, screen printing, microcontact (wave)-printing, drop or zone casting, or other known techniques).

The polymers of the invention can be used in integrated circuits comprising a plurality of OTFTs, as well as in various electronic articles. Such articles include, for example, radio-frequency identification (RFID) tags, backplanes for flexible displays (for use in, for example, personal computers, cell phones, or handheld devices), smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-, mechanical- or temperature sensors), especially photodiodes, or security devices and the like.

A further aspect of the present invention is an organic semiconductor material, layer or component comprising one or more polymers of the present invention. A further aspect is the use of the polymers or materials of the present invention in an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET). A further aspect is an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET) comprising a polymer or material of the present invention.

The polymers of the present invention are typically used as organic semiconductors in form of thin organic layers or films, preferably less than 30 microns thick. Typically the semiconducting layer of the present invention is at most 1 micron (=1 μm) thick, although it may be thicker if required. For various electronic device applications, the thickness may also be less than about 1 micron thick. For example, for use in an OFET the layer thickness may typically be 100 nm or less. The exact thickness of the layer will depend, for example, upon the requirements of the electronic device in which the layer is used.

For example, the active semiconductor channel between the drain and source in an OFET may comprise a layer of the present invention.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,     -   a drain electrode,     -   a gate electrode,     -   a semiconducting layer,     -   one or more gate insulator layers, and     -   optionally a substrate, wherein the semiconductor layer         comprises one or more polymers of the present invention.

The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a polymer of the present invention located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.

The OFET device can be a top gate device or a bottom gate device.

Suitable structures and manufacturing methods of an OFET device are known to the person skilled in the art and are described in the literature, for example in WO03/052841.

The gate insulator layer may comprise for example a fluoropolymer, like e.g. the commercially available Cytop 809M®, or Cytop 107M® (from Asahi Glass). Preferably the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380). Other suitable fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont), or Fluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377).

The semiconducting layer comprising a polymer of the present invention may additionally comprise at least another material. The other material can be, but is not restricted to another polymer of the present invention, a semi-conducting polymer, a polymeric binder, organic small molecules different from a polymer of the present invention, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles (Au, Ag etc.), and insulator materials like the ones described for the gate dielectric (PET, PS etc.). As stated above, the semiconductive layer can also be composed of a mixture of one or more polymers of the present invention and a polymeric binder. The ratio of the polymers of the present invention to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA). With this technique, a degradation of the electrical performance can be avoided (cf. WO2008/001123A1).

The polymers of the present invention are advantageously used in organic photovoltaic (PV) devices (solar cells). Accordingly, the invention provides PV devices comprising a polymer according to the present invention. A device of this construction will also have rectifying properties so may also be termed a photodiode. Photoresponsive devices have application as solar cells which generate electricity from light and as photodetectors which measure or detect light.

The PV device comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode (electrode),

(f) a substrate.

The photoactive layer comprises the polymers of the present invention. Preferably, the photoactive layer is made of a conjugated polymer of the present invention, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor. As stated above, the photoactive layer may also contain a polymeric binder. The ratio of the polymers of formula I to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA).

For heterojunction solar cells the active layer comprises preferably a mixture of a polymer of the present invention and a fullerene, such as, for example, [60]PCBM (=6,6-phenyl-C₆₁-butyric acid methyl ester), or [70]PCBM, in a weight ratio of 1:1 to 1:3. The fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C₆₀) and the related “spherical” fullerenes as well as carbon nanotubes. Fullerenes may be selected from those known in the art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₉ to C₉₆. Most preferably the fullerene is C₆₉ or CM, such as [60]PCBM, or [70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics. The acceptor material can also be a material selected from the group consisting of any semi-conducting polymer, such as, for example, a polymer of the present invention, provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a polymer of the present invention as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-Blodgett (“LB”) method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer. Instead of toluene, which is typical, a dispersion agent such as chlorobenzene is preferably used as a solvent. Among these methods, the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, the casting method and ink jet printing method, the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum. Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006) and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)

(f) optionally an extra electrode to match the energy level,

(g) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,

(h) a photoactive layer,

(i) optionally a smoothing layer,

(j) an anode (electrode),

(k) a substrate.

The PV device can also be processed on a fiber as described, for example, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or films comprising the polymers of the present invention can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US2003/0021913.

It is another object of the present invention to provide compounds, which show high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability, when used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

In a further embodiment the present invention relates to compounds of the formula

wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group of formula

wherein R¹, R², R⁶⁰¹ and R⁶⁰² are as defined above,

p is 0, or 1, q is 0, or 1;

A¹ and A² are independently of each other a group of formula

a is 0, 1, 2, or 3, b is 0, 1, 2, or 3; c is 0, 1, 2, or 3;

A³, A⁴, A⁵ and A^(5′) are independently of each other a group of formula —[Ar⁴]_(k)—[Ar⁵]_(l)—[Ar⁶]_(r)—[Ar⁷]_(z)—;

k′ is 0, 1, 2, or 3; l is 0, 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3;

R¹⁰ is hydrogen, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted one or more times by E″ and/or interrupted one or more times by D″,

COO—C₁-C₁₈alkyl, C₄-C₁₈cycloalkyl group, C₄-C₁₈cycloalkyl group, which is substituted by G″, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈thioalkoxy, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E″ and/or interrupted by D″, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl, which is substituted by G″, or a group of formulae IVa to IVm,

wherein R²² to R²⁶ and R²⁹ to R⁵⁸ represent independently of each other H, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E″ and/or interrupted by D″, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G″, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G″, a C₄-C₁₈cycloalkyl group, a C₄-C₁₈cycloalkyl group, which is substituted by G″, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E″ and/or interrupted by D″, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl, which is substituted by G″,

R²⁷ and R²⁸ are independently of each other hydrogen, C₁-C₂₅alkyl, halogen, cyano or C₇-C₂₅aralkyl, or R²⁷ and R²⁸ together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms,

R⁵⁹ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,

D″ is —CO—, —COO—, —S—, —O—, or NR^(112″)—,

E″ is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR^(112″)R^(113″), —CONR^(112″)R^(113″), or halogen,

G″ is E″, or C₁-C₁₈alkyl, and

R^(112″) and R^(113″) are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;

R²¹⁴ and R²¹⁵ are independently of each other hydrogen, C₁-C₁₈alkyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CN or COOR²¹⁶;

R²¹⁶ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl or C₂-C₂₀heteroaryl;

R²¹⁸ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,

Ar¹, Ar², Ar³ Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other a group of formula (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIg), (XIh), (XIi), (XIj), (XIk), (XIl), (XIm), (XIn), (XIo), (XIpa), (XIpb), (XIq), (XIr), (XIs), (XIt), (XIu), (XIv), (XIw), (XIx), (XIy), (XIz), (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), (XIIk), (XIIl), such as, for example, (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf), (XIIIg), (XIIIh), (XIIIi), (XIIIj), (XIIIk), and (XIIIl); or (XIV), such as, for example, (XIVa); (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr), (XVs), such as, for example, (XVsa), (XVsb), and (XVsc); (XVt), such as, for example, (XVta), (XVtb), and (XVuc), and (XVu).

The structure represented by formula

can be bonded in two ways to the groups of formula A³, A⁴, A⁵ and A^(5′):

(the dotted line represents the bonding to the groups of formula A³, A⁴, A⁵ and A^(5′)). Both possibilities shall be covered by formula (I).

Preferably, the compound is a compound of the formula A¹-Y-A³-Y¹⁵-A² (VIIIa), A¹-Y-A³-Y¹⁵-A⁴-Y¹⁶-A² (VIIIb), or A¹-Y-A³-Y¹⁵-A⁴-Y¹⁶-A⁵-Y¹⁷-A² (VIIIc), A¹-A³-Y-A⁴-A² (IXa), A¹-A³-Y-A⁴-Y¹⁵-A⁵-A² (IXb), or A¹-A³-Y-A⁴-Y₁₅-A⁵-Y¹⁷-A^(5′)-A² (IXc), wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group of formula

wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of each other H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—, or

R¹ and R² form together a group

and R⁶⁰¹ and R⁶⁰² are independently of each other hydrogen, or C₁-C₂₅ alkyl, especially hydrogen.

A¹ and A² are as defined above,

A³, A⁴, A⁵ and A^(5′) are independently of each other a group of formula

wherein

R³, R^(3′), R⁴ and R^(4′) are independently of each other hydrogen, or C₁-C₂₅alkyl;

R⁸ and R^(8′) are independently of each other hydrogen, or C₁-C₂₅alkyl;

R¹¹⁴ is a C₁-C₃₈alkyl group;

R²⁰¹ is a C₁-C₃₈alkyl group; and

R²⁰² and R^(203′) are independently of each other hydrogen or C₁-C₂₅alkyl.

R¹ and R² are especially a group of formula

very especially a group of formula

R¹ and R² may be the same, but are preferably the same.

The group of formula (I) is preferably a group of formula

especially (Ia).

In a preferred embodiment A³, A⁴, A⁵ and A^(5′) are independently of each other a group of formula (XVb), (XVb′), (XVh), (XVh′), (XVi), (XVi′), (XVu′), (XVu″), and (XVu′″). In a particularly preferred embodiment A³, A⁴, A⁵ and A^(5′) are selected from groups of formula (XVb), (XVc), (XVu′), (XVu″), and (XVu′″).

In a preferred embodiment of the present invention A¹ and A² are independently of each other a group of formula H,

In a preferred embodiment the present invention is directed to compounds of formula A¹-A³-Y-A⁴-A² (IXa), wherein Y is a group of formula

In said embodiment A¹-A³- and A⁴-A²- are a group of formula:

i)

(R³ and R⁴ may be different, but are preferably the same and are H, or C₁-C₂₅alkyl; R²⁰¹ is a C₁-C₃₈alkyl group);

ii)

(R³ and R⁴ may be different, but are preferably the same and are H, or C₁-C₂₅alkyl; R²⁰¹ is a C₁-C₃₈alkyl group);

iii)

(R³ and R^(3′) may be different, but are preferably the same and are H, or C₁-C₂₅alkyl; R⁴ and R^(4′) may be different, but are preferably the same and are H, or C₁-C₂₅alkyl).

Examples of particular preferred compounds of formula IX are shown below:

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each other hydrogen or C₁-C₂₅alkyl; and R²⁰¹ is a C₁-C₃₈alkyl group. R³, R^(3′), R⁴ and R^(4′) are preferably hydrogen.

Compounds A-1, A-2, A-5 and A-11 are most preferred.

A¹-A³-Y-A³-A¹ (IXa) may be prepared by reacting a compound of formula A¹-A³-X¹⁶ with a compound of formula X^(16′)—Y—X^(16′), X^(16′) is —B(OH)₂, —B(OH)₃—, —BF₃, —B(OY¹)₂,

and X¹⁶ is halogen, such as, for example, Br, or I.

The Suzuki reaction is typically conducted at about 0° C. to 180° C. in an aromatic hydrocarbon solvent such as toluene, xylene. Other solvents such as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon. An aqueous base, preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scavenger. A condensation reaction may take 0.2 to 100 hours. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252.

In the above Suzuki coupling reactions the halogen X¹⁶ on the halogenated reaction partner can be replaced with the X^(16′) moiety and at the same time the X^(16′) moiety of the other reaction partner is replaced by X¹⁶.

The synthesis of the corresponding diketopyrrolopyrrole intermediates is, for example, described in R. A. J. Janssen et al., Macromol. Chem. Phys. 2011, 212, 515-520, US2010/0326225 and EP11179840.1.

Accordingly, the present invention also relates to an organic semiconductor material, layer or component, comprising a compound of formula VIII, or IX and to a semiconductor device, comprising a compound of formula VIII, or IX and/or an organic semiconductor material, layer or component.

The semiconductor is preferably an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor. The structure and the components of the OFET device has been described in more detail above.

Accordingly, the invention provides organic photovoltaic (PV) devices (solar cells) comprising a compound of the formula VIII, or IX.

The structure of organic photovoltaic devices (solar cells) is, for example, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.

The PV device comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode (electrode),

(f) a substrate.

The photoactive layer comprises the compounds of the formula VIII, or IX. Preferably, the photoactive layer is made of a compound of the formula VIII, or IX, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor. As stated above, the photoactive layer may also contain a polymeric binder. The ratio of the small molecules of formula VIII, or IX to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA).

The fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C₆₀) and the related “spherical” fullerenes as well as carbon nanotubes. Fullerenes may be selected from those known in the art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₉ to C₉₆. Most preferably the fullerene is C₆₉ or C₇₀, such as [60]PCBM, or [70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics. The acceptor material can also be a material selected from the group consisting of another compounds of formula VIII, or IX, or any semi-conducting polymer, such as, for example, a polymer of formula I, provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a compound of the formula VIII, or IX, as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-Blodgett (“LB”) method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer. Instead of toluene, which is typical, a dispersion agent such as chlorobenzene is preferably used as a solvent. Among these methods, the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, the casting method and ink jet printing method, the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum. Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006) and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)

(f) optionally an extra electrode to match the energy level,

(g) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,

(h) a photoactive layer,

(i) optionally a smoothing layer,

(j) an anode (electrode),

(k) a substrate.

The PV device can also be processed on a fiber as described, for example, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or films comprising the compounds of the formula VIII, or IX can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US2003/0021913.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,     -   a drain electrode,     -   a gate electrode,     -   a semiconducting layer,     -   one or more gate insulator layers, and     -   optionally a substrate, wherein the semiconductor layer         comprises a compound of formula VIII, or IX.

The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a compound of formula VIII, or IX located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.

The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight. Weight-average molecular weight (Mw) and polydispersity (Mw/Mn=PD) are determined by High Temperature Gel Permeation Chromatography (HT-GPC) [Apparatus: GPC PL 220 from Agilent Technologies (Santa Clara, Calif., USA) yielding the responses from refractive index (RI), Chromatographic conditions: Column: 3 “PLgel Mixed B” columns from Agilent Technologies (Santa Clara, Calif., USA); with an average particle size of 10 □μm (dimensions 300×7.5 mm I.D.) Mobile phase: 1,2,4-trichlorobenzene (for GPC, AppliChem, Darmstadt, Germany) stabilised by butylhydroxytoluene (BHT, 1 g/l), Chromatographic temperature: 150° C.; Mobile phase flow: 1 ml/min; Solute concentration: about 1 mg/ml; Injection volume: 200 μl; Detection: RI, Procedure of molecular weight calibration: Relative calibration is done by use of a EasiVial calibration kit from Agilent Technologies (Santa Clara, Calif., USA) containing 12 narrow polystyrene calibration standards spanning the molecular weight range from 6,035,000 Da-162 Da, i. e., PS 6,035,000, PS 3,053,000, PS 915,000, PS 483,000, PS 184,900, PS 60,450, PS 19,720, PS 8,450, PS 3,370, PS 1,260, PS 580, PS 162 Da. A polynomic calibration is used to calculate the molecular weight.

All polymer structures given in the examples below are idealized representations of the polymer products obtained via the polymerization procedures described. If more than two components are copolymerized with each other sequences in the polymers can be either alternating or random depending on the polymerisation conditions.

EXAMPLES Example 1 Synthesis of Polymer P-1

a) The synthesis of compound 100 is described, for example, in WO2009115413.

862 mg (20.55 mmol) lithium hydroxide monohydrate in 10 ml water are added to 2.5 g 6.85 mmol) of compound 100 and 5.46 g (14.04 mmol) benzyl(triphenyl)phosphonium chloride in 40 ml dichloromethane. The reaction mixture is stirred at 25° C. for 4 h. The organic phase is separated, the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over magnesium sulphate and filtered. The solvent is distilled off and the product 101 is then purified by two successive column chromatographies (eluent: toluene/cyclohexane 1:10 and then toluene/cyclohexane 1:1).

Yield: 52% (1.89 g, white powder).

¹H NMR (400 MHz, CDCl₃): δ=7.75 (s, 1H), 7.47-7.22 (m, 10H), 6.86 (s, 1H), 5.81 (d, J=7.0 Hz, 1H), 4.96 (d, J=7.2 Hz, 1H), 0.46 (s, 9H), 0.30 (s, 9H).

¹³C NMR (100 MHz, CDCl₃): δ=152.3, 142.4, 141.9, 141.3, 140.5, 138.7, 135.6, 131.1, 128.9 (2C), 128.7 (2C), 128.2 (2C), 128.1 (2C), 127.5, 127.2, 125.8 (2C), 125.2, 116.2, 94.1, 58.4, −0.2 (3C), −0.4 (3C). GC/MS: (CI pos.): 529.28 (MH⁺).

b) In a 100 mL flask previously flushed with nitrogen and equipped with a condenser and a nitrogen bubbler is introduced compound 101 (1.3 g, 2.46 mmol) and tetrahydrofurane (THF, 30 mL). A solution of tetrabutylammonium fluoride trihydrate (1.71 g, 5.41 mmol) in tetrahydrofurane (10 mL) is then added and the mixture is stirred for 2 h at room temperature. After that time water (100 mL) is added, and the product is extracted with dichloromethane. The combined organic phases are then dried over magnesium sulphate and filtered. The solvent is distilled off and the product 102 is then purified by column chromatography (eluent: cyclohexane/toluene 4:1). Yield: 96% (910 mg, white powder).

¹H NMR (400 MHz, CDCl₃): δ=7.60 (1H, d, J=5.5 Hz), 7.44-7.24 (12H, m), 6.74 (1H, d, J=5.5 Hz), 5.79 (1H, d, J=7.5 Hz), 4.93 (1H, d, J=7.5 Hz); GC/MS: (CI pos.): 385.16 (MH⁺).

c) 0.52 g (2.29 mmol) 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) are added to 0.8 g (2.08 mmol) of compound 102 in 20 ml chlorobenzene. The reaction mixture is refluxed for 2 h under nitrogen, and then cooled to room temperature. Dichloromethane is added and the reaction mixture is washed with a sodium hydrogen carbonate solution. The organic phase is dried with magnesium sulphate and filtered. The solvent is evaporated on a rotary evaporator. The crude product is then purified by column chromatography (cyclohexane/toluene 4:1) to get product 103 as a white powder. Yield: 88% (702 mg, white powder).

¹H NMR (400 MHz, CDCl₃): δ=7.88 (1H, d, J=5.3 Hz), 7.70 (2H, m), 7.61-7.56 (5H, m), 7.53 (1H, d, J=5.5 Hz, 1H), 7.37-7.28 (4H, m), 6.97 (1H, d, J=5.3 Hz). GC/MS: (CI pos.): 383.21 (MH⁺).

d) In a 3-neck flask equipped with a condenser and a nitrogen bubbler is introduced compound 103 (1.02 g, 2.67 mmol). The flask is flushed with nitrogen and tetrahydrofuran (THF) is added (80 mL). The solution is then cooled to −78° C. and a n-butyllithium solution (2.67 mL, 6.67 mmol, 2.5 M solution) is added dropwise. The resulting mixture is stirred for 1 h 20 at −78° C. After that time 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.49 g, 8.00 mmol) is added at −78° C. After 20 minutes at −78° C., the mixture is allowed to warm to room temperature and stirred 2 hours at room temperature. Then, water is added at 0° C. and the product is extracted with tert-butyl-methyl-ether (100 mL) and dichloromethane (two times 100 mL). The combined organic fractions are dried over anhydrous sodium sulphate, filtered and concentrated on rotary evaporator. The crude solid is triturated in hot acetonitrile and left to cool to 0° C. The white solid (product 104) is filtered and dried under vacuum. Yield: 72% (1.21 g, white powder).

¹H-NMR (400.1 MHz, CDCl₃): δ=8.40 (1H, s), 7.62-7.54 (7H, m), 7.52 (1H, s), 7.32-7.26 (3H, m), 1.43 (12H, s), 1.33 (12H, s). ¹³C NMR (100 MHz, CDCl₃): δ=149.1, 147.2, 135.9, 134.4, 133.6, 132.4, 131.8, 130.8, 130.4 (2C), 130.3, 129.2 (2C), 128.4 (2C), 128.2, 127.7, 126.2 (2C), 125.7, 121.4, 119.1, 84.6 (2C), 84.3 (2C), 24.9 (4C), 24.7 (4C).

e) The synthesis of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 107 is, for example, described in WO2008/000664 and Y. Geerts; Tetrahedron 66 (2010) 1837-1845. In a flask equipped with a condenser, a mechanical stirrer, a nitrogen bubbler and a thermometer is introduced the bis-boronic ester 104 from step d) (400 mg, 0.63 mmol) and 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 107 (545 mg, 0.60 mmol). The flask is flushed with nitrogen and dry THF (30 mL) is added by syringe. The resulting red solution is heated to 60° C. and a solution of palladium(II) acetate (4.0 mg, 0.018 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (20.7 mg, 0.072 mmol) in 10 mL THF is added. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (159 mg, 3.78 mmol) is added in a single portion at 60° C. and is stirred at reflux temperature for 4 hours. The reaction mixture is poured into ethanol (300 mL) and the precipitate is filtered on a Büchner funnel. The solid is then washed with 200 mL ethanol and 200 mL deionised water. The filtered solid is then put in a flask containing 150 mL chloroform and 150 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 60° C. overnight. The organic phase is washed with 100 mL water, and two thirds of the chloroform is then evaporated. Ethanol is added to precipitate the product, which is filtered on a Büchner funnel, washed with 300 mL ethanol and dried in the oven. The treatment with sodium cyanide is then repeated a second time. The dried solid is then purified by soxhlet extraction, first with tetrahydrofuran (200 mL, 6 h). The fraction soluble in tetrahydrofuran is discarded and the remaining solid is then subjected to soxhlet extraction with chloroform (200 mL, 7 h). The green solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-1 (598 mg, yield 88%). High temperature GPC: M_(w)=97700, M_(n)=46200, PD=2.11.

Example 2 Synthesis of Polymer P-2

a) In a flask equipped with a condenser, is introduced compound 105 (7.00 g, 8.05 mmol), sodium iodide (4.83 g, 32.2 mmol) and copper iodide (153 mg, 0.81 mmol). The flask is flushed with nitrogen (3× vacuum/nitrogen) and 1,4-dioxane (175 mL) is added, followed by the trans-N,N-dimethylcyclohexane-1,2-diamine (229 mg, 1.61 mmol). The mixture is then stirred at reflux overnight. After that time the mixture is poured into 350 mL water. 350 mL of a 1 M NaOH aqueous solution is added, and the product is extracted with dichloromethane. The combined organic phases are dried over sodium sulphate and filtered. Solvents are removed on rotary evaporator. Analysis shows an unseparable mixture of product and starting material. The crude product is then subjected several times to similar reaction conditions until conversion is >97%. The crude product is then purified by column chromatography and recrystallization in isopropanol to afford the compound 106 as a red solid.

¹H-NMR (400.1 MHz, CDCl₃): □δ□=8.89 (2H, d, J=8.5 Hz), 7.38 (2H, dd, J=8.5, 1.8 Hz), 7.09 (2H, d, J=1.8 Hz), 3.60 (4H, d, J=7.2 Hz), 1.87 (2H, m), 1.38-1.20 (48H, m), 0.90-0.83 (12H, m); ¹³C NMR (100 MHz, CDCl₃): δ=167.9 (2C), 145.8 (2C), 132.9 (2C), 131.3 (2C), 130.9 (2C), 121.0 (2C), 117.2 (2C), 99.0 (2C), 44.6 (2C), 36.1 (2C), 31.9 (2C), 31.8 (2C), 31.5 (4C), 30.0 (2C), 29.7 (2C), 29.6 (2C), 29.3 (2C), 26.4 (2C), 26.3 (2C), 22.7 (2C), 22.6 (2C), 14.1 (4C)

b) In a flask equipped with a condenser, a mechanical stirrer, a nitrogen bubbler and a thermometer is introduced the bis-boronic ester 104 (466 mg, 0.73 mmol) and (3E)-1-(2-hexyldecyl)-3-[1-(2-hexyldecyl)-6-iodo-2-oxo-indolin-3-ylidene]-6-iodo-indolin-2-one 106 (674 mg, 0.70 mmol). The flask is flushed with nitrogen and dry THF (40 mL) is added by syringe. The resulting red solution is heated to 60° C. and a solution of palladium(II) acetate (4.7 mg, 0.021 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (24.1 mg, 0.084 mmol) in 10 mL THF is added. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (185 mg, 4.41 mmol) is added in a single portion at 60° C. and is stirred at reflux temperature for 5 hours. The reaction mixture is poured into ethanol (400 mL) and the precipitate is filtered on a Büchner funnel. The solid is then washed with 200 mL ethanol and 200 mL deionised water. The filtered solid is then put in a flask containing 150 mL chloroform and 150 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 55° C. overnight. The organic phase is washed three times with 100 mL water, and the chloroform is then evaporated. Ethanol is added to precipitate the product, which is filtered on a Büchner funnel, washed with 200 mL water and 50 mL ethanol and dried in the oven. The treatment with sodium cyanide is then repeated a second time. The dried solid is then purified by soxhlet extraction, first with acetone (200 mL, 2 h) and then with tert-butyl-methyl-ether (200 mL, 5 h). The fractions soluble in acetone and tert-butyl-methyl-ether are discarded and the remaining solid is then subjected to soxhlet extraction with THF (200 mL, 5 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-2 (659 mg, yield 86%). High temperature GPC: M_(w)=24600, Mn=15500, PD=1.58.

Example 3 Synthesis of Polymer P-3

The synthesis of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 108 is, for example, described in WO2011/144566.

In a flask equipped with a condenser, a mechanical stirrer, a nitrogen bubbler and a thermometer is introduced compound 104 (400 mg, 0.63 mmol) and 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-butyloctyppyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 108 (458 mg, 0.60 mmol). The flask is flushed with nitrogen and dry THF (30 mL) is added by syringe. The resulting red solution is heated to 60° C. and a solution of palladium(II) acetate (4.0 mg, 0.018 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (20.7 mg, 0.072 mmol) in 10 mL THF is added. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (159 mg, 3.78 mmol) is added in a single portion at 60° C. and the mixture is stirred at reflux temperature for 4 hours. The reaction mixture is poured into ethanol (300 mL) and the precipitate is filtered on a Büchner funnel. The solid is then washed with 200 mL ethanol and 200 mL deionised water. The filtered solid is then put in a flask containing 150 mL chloroform and 150 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 60° C. overnight. The organic phase is washed with water, and two thirds of the chloroform is then evaporated. Ethanol is added to precipitate the product, which is filtered on a Büchner funnel, washed with 300 mL ethanol and dried in the oven. The treatment with sodium cyanide is then repeated a second time. The dried solid is then purified by soxhlet extraction. Fractions soluble in acetone, tert-butyl-methyl-ether and cyclohexane are discarded. Soxhlet extraction is then performed with tetrahydrofuran, and the green solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-3 (510 mg, yield 86%). High temperature GPC: M_(w)=91400, M_(n)=33100, PD=2.76.

Application Examples 1, 2 and 3

Photovoltaic Application of the Semiconducting Polymers:

The solar cell has the following structure: Al electrode/LiF layer/organic layer, including compound of the invention/[poly(3,4-ethylenedioxy-thiophene) (PEDOT)/poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate. The solar cells are made by spin coating a layer of the PEDOT-PSS on a pre-patterned ITO on glass substrate. Then a 1:2 mixture of the semiconducting polymer (1% by weight): [70]PCBM (a substituted C₇₀ fullerene) is spin coated (organic layer). LiF and Al are sublimed under high vacuum through a shadow-mask.

Solar Cell Performance

The solar cell is measured in homemade solar light simulator with Osram Xenon Short Arc XBO 450 W lamp. Then with the External Quantum Efficiency (EQE) graph the current is estimated under AM1.5 conditions.

The OPV performances of Semiconducting polymers are shown in the table below:

Appl. Example Semiconductor Solvent Jsc, mA/cm² Voc, V FF, % η, % 1 Polymer P-1   CHCl₃/oDCB (9:1) −9.61 0.76 50.1 3.62 2 Polymer P-2 Xylene/Tetraline (8:2) −3.01 0.94 56.0 1.55 3 Polymer P-3   CHCl₃/oDCB (8:2) −12.00 0.81 49.0 4.73

Application Examples 4, 5 and 6

OFET Application of the Semiconducting Polymers:

Semiconductor Film Deposition:

Siliconwafers (Si n- -(425±40 μm)) with a 230 nm thick SiO₂ dielectric and patterned indium tin oxide (15 nm)/gold (30 nm) contacts (L=20, 10, 5, 2.5 μm, W=0.01 m; Fraunhofer IPMS (Dresden)) are prepared by standard cleaning by washing with acetone and i-propanol followed by oxygen plasma treatment for 30 minutes. The substrates are transferred in a glove box. An octyltrichlorsilane (OTS) monolayer is grown on the dielectric surface by putting the substrates in a 50 mM solution of octyltrichlorosilane (OTS) in trichloroethylene for 1 h. After monolayer growth, the substrates are washed with toluene to remove physisorbed silane. The semiconductor is dissolved in a proper solvent in a concentration 0.75% by weight at 80° C. and spin-coated at 1500 rpms for 60 s onto the substrates.

OFET Measurement:

OFET transfer and output characteristics are measured on an Agilent 4155C semiconductor parameter analyzer. The devices are annealed in a glovebox at 150° C. for 15 minutes before the measurements are done in a glove box under a nitrogen atmosphere at room temperature. For p-type transistors the gate voltage (V_(g)) varies from 10 to −30 V and at drain voltage (V_(d)) equal to −3 and −30V for the transfer characterisation. For the output characterization V_(d) is varied from 0 to −30V at V_(g)=0, −10, −20, −30 V.

Appl. Mobility, Example Semiconductor Solvent cm²/Vs On/off 4 Polymer P-1 oDCB 1.80 · 10⁻² 1.10 · 10⁵ 5 Polymer P-2 oDCB 2.00 · 10⁻³ 4.30 · 10⁵ 6 Polymer P-3 oDCB 6.80 · 10⁻³ 1.80 · 10⁶ 

The invention claimed is:
 1. A polymer, comprising; a repeating unit of formula (I):

where R¹ and R² are each independently H, F, C₁-C₁₈ alkyl, C₁-C₁₈alkyl which is substituted by E′ and/or interrupted by D′, C₆-C₂₄ aryl, C₆-C₂₄ aryl which is substituted by G′, C₂-C₂₀ heteroaryl, C₂-C₂₀ heteroaryl which is substituted by G′, or R¹ and R² together form a group

wherein R²⁰⁵, R²⁰⁶, R^(206′), R²⁰⁷, R²⁰⁸, R^(208′), R²⁰⁹ and R²¹⁰ are each independently H, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl which is substituted by E′ and/or interrupted by D′, C₁-C₁₈ alkoxy, or C₁-C₁₈ alkoxy which is substituted by E′ and/or interrupted by D′, C₁-C₁₈ fluoroalkyl, C₆-C₂₄ aryl, C₆-C₂₄ aryl which is substituted by G′, C₂-C₂₀ heteroaryl, C₂-C₂₀ heteroaryl which is substituted by G′, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₇-C₂₅ aralkyl, C₇-C₂₅ aralkyl which is substituted by G′; CN, or —CO—R²⁸, R⁶⁰¹ and R⁶⁰² are each independently H, halogen, C₁-C₂₅ alkyl, C₃-C₁₂ cycloalkyl, C₂-C₂₅ alkenyl, C₂-C₂₅ alkynyl, C₆-C₂₄ aryl, C₆-C₂₄ aryl which is substituted by G′, C₇-C₂₅ aralkyl, or C₇-C₂₅ aralkyl which is substituted by G′; D′ is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR⁶⁵—, —SiR⁷⁰R⁷¹—, —POR⁷²—, —CR⁶³═CR⁶⁴—, or —C≡C—, and E′ is —OR⁶⁹, —SR⁶⁹, —NR⁶⁵R⁶⁶, —COR⁶⁸, —COOR⁶⁷, —CONR⁶⁵R⁶⁶, —CN, CF₃, or halogen, G′ is E′, C₁-C₁₈ alkyl, or C₁-C₁₈ alkyl which is interrupted by —O—, R²⁸ is H; C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, R⁶³ and R⁶⁴ are each independently C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—; R⁶⁵ and R⁶⁶ are each independently C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—; or R⁶⁵ and R⁶⁶ together form a five or six membered ring, R⁶⁷ is C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, R⁶⁸ is H; C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, R⁶⁹ is C₆-C₁₈ aryl; C₆-C₁₈ aryl, which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, R⁷⁰ and R⁷¹ are each independently C₁-C₁₈ alkyl, C₆-C₁₈ aryl, or C₆-C₁₈ aryl, which is substituted by C₁-C₁₈ alkyl, and R⁷² is C₁-C₁₈ alkyl, C₆-C₁₈ aryl, or C₆-C₁₈ aryl, which is substituted by C₁-C₁₈ alkyl.
 2. The polymer according to claim 1,

wherein R¹ and R² are each independently a group of formula

where R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are each independently H, CN, F, CF₃, C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, or R¹ and R² together form a group

and R⁶⁰¹ and R⁶⁰² are each independently hydrogen, or C₁-C₂₅ alkyl.
 3. The polymer according to claim 1, which is a polymer of formula

or a polymer, comprising repeating units of formulae

wherein n ranges from 4 to 1000, A is a repeating unit of the formula (I), and —COM¹- is a repeating unit of

where k is 0, 1, 2, or 3; l is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3; Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are each independently of a formula:

where X¹ is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—, —C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

where X^(1′) is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—, —C(R¹⁰⁶)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are each independently hydrogen, halogen, halogenated C₁-C₂₅ alkyl, cyano, C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅ arylalkyl, or C₁-C₂₅ alkoxy; R¹⁰⁴ and R^(104′) are each independently hydrogen, cyano, COOR¹⁰³, C₁-C₂₅ alkyl, or C₆-C₂₄ aryl or C₂-C₂₀ heteroaryl, R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) are each independently hydrogen, halogen, halogenated C₁-C₂₅ alkyl, cyano, C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅ arylalkyl, or C₁-C₂₅ alkoxy; R⁷, R^(7′), R⁹ and R^(9′) are each independently hydrogen, C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅ arylalkyl, R⁸ and R^(8′) are each independently hydrogen, C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; or C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅ arylalkyl, R¹¹ and R^(11′)are each independently C₁-C₂₅ alkyl group, C₇-C₂₅ arylalkyl, or a phenyl group, which is optionally substituted one to three times with C₁-C₈ alkyl and/or C₁-C₈ alkoxy; R¹² and R^(12′) are each independently hydrogen, halogen, cyano, C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, C₁-C₂₅ alkoxy, C₇-C₂₅ arylalkyl, or

where R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; or R¹⁰⁴ and R^(104′) are each independently hydrogen, C₁-C₁₈ alkyl, C₆-C₁₀ aryl, which is optionally substituted by G, or C₂-C₈ heteroaryl, which is optionally substituted by G, R¹⁰⁵, R^(105′), R¹⁰⁶ and R^(106′)are each independently hydrogen, halogen, cyano, C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅ arylalkyl, or C₁-C₁₈ alkoxy, R¹⁰⁷ is hydrogen, C₇-C₂₅ arylalkyl, C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ perfluoroalkyl; C₁-C₂₅ alkyl; which is optionally interrupted by —O—, or —S—; or —COOR¹⁰³; R¹⁰⁸ and R¹⁰⁹ are each independently H, C₁-C₂₅ alkyl, C₁-C₂₅ alkyl which is substituted by E and/or interrupted by D, C₇-C₂₅ arylalkyl, C₆-C₂₄ aryl, C₆-C₂₄ aryl which is substituted by G, C₂-C₂₀ heteroaryl, C₂-C₂₀ heteroaryl which is substituted by G, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₁-C₁₈ alkoxy, C₁-C₁₈ alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅ aralkyl, or R¹⁰⁸ and R¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, where R¹¹⁰ and R¹¹¹ are each independently H, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄ aryl, C₆-C₂₄ aryl which is substituted by G, or C₂-C₂₀ heteroaryl, or C₂-C₂₀ heteroaryl which is substituted by G, or R¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, which is optionally substituted by C₁-C₁₈ alkyl, C₁-C₁₈ alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄ aryl, C₆-C₂₄ aryl which is substituted by G, C₂-C₂₀ heteroaryl, C₂-C₂₀ heteroaryl which is substituted by G, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₁-C₁₈ alkoxy, C₁-C₁₈ alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅ aralkyl, D is —CO—, —COO—, —S—, —O—, or —NR^(112′)—, E is C₁-C₈ thioalkoxy, C₁—C alkoxy, CN, —NR^(112′)R^(113′), —CONR^(112′)R^(113′), or halogen, G is E, or C₁-C₁₈ alkyl, and R^(112′) and R^(113′) are each independently H; C₆-C₁₈aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, R¹¹⁵ and R^(115′) are each independently hydrogen, halogen, cyano, C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, C₁-C₂₅ alkoxy, C₇-C₂₅ arylalkyl, or

where R¹¹⁶ is a C₁-C₁₀ alkyl group, or a tri(C₁-C₈alkyl)silyl group; R¹¹⁷ and R^(117′) are each independently C₁-C₂₅ alkyl group, C₇-C₂₅ arylalkyl, or a phenyl group, which is optionally substituted one to three times with C₁-C₈ alkyl and/or C₁-C₈ alkoxy; R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are each independently hydrogen, halogen, halogenated C₁-C₂₅ alkyl, cyano, C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C₇-C₂₅ arylalkyl, or C₁-C₂₅ alkoxy; R¹²² and R^(122′) are each independently hydrogen, C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; or C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅ arylalkyl, R²⁰¹ is selected from the group consisting of hydrogen, a C₁-C₁₀₀alkyl group, —COOR¹⁰³, a C₁-C₁₀₀ alkyl group substituted by one or more halogen atoms, a hydroxyl group, a nitro group, —CN, a C₆-C₁₈aryl group and/or interrupted by —O—, —COO—, —OCO— or —S—; a C₇-C₂₅ arylalkyl group, a carbamoyl group, a C₅-C₁₂ cycloalkyl group, which is optionally substituted one to three times with C₁-C₁₀₀alkyl and/or C₁-C₁₀₀alkoxy, a C₆-C₂₄aryl group, which is optionally substituted one to three times with C₁-C₁₀₀ alkyl, C₁-C₁₀₀ thioalkoxy, and/or C₁-C₁₀₀ alkoxy; and pentafluorophenyl; R¹⁰³ and R¹¹⁴ are each independently C₁-C₂₅ alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, and R²⁰² and R²⁰³ are each independently selected from the group consisting of H, F, —CN, C₁-C₁₀₀alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; and C₁-C₁₀₀ alkoxy.
 4. The polymer according to claim 1, comprising: units of

wherein A is a repeating unit of the formula (I), and —COM¹- is a repeating unit of

where R³, R^(3′), R⁴ and R^(4′) are each independently hydrogen, or C₁-C₂₅ alkyl; R⁸ and R^(8′) are each independently hydrogen, or C₁-C₂₅ alkyl; R¹¹⁴ is a C₁-C₃₈ alkyl group; R²⁰¹ is a C₁-C₃₈ alkyl group; and R²⁰² and R^(203′) are each independently hydrogen or C₁-C₂₅ alkyl.
 5. The polymer according to claim 3, wherein R¹ and R² are each independently of formula

where R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are each independently H, CN, F, CF₃, C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, or R¹ and R² together form a group

R⁶⁰¹ and R⁶⁰² are independently selected from the group consisting of a C₁-C₂₅alkyl group and hydrogen; and

is of formula

where R³, R^(3′), R⁴ and R^(4′) are each independently hydrogen or C₁-C₂₅ alkyl; and R²⁰¹ is a C₁-C₃₈ alkyl group.
 6. The polymer according to claim 4, which is a polymer of formula

where n is 4 to 1000; R³, R^(3′), R⁴ and R^(4′)are each independently hydrogen or C₁-C₂₅ alkyl; R²⁰¹ is a C₁-C₃₈ alkyl group, and R⁶⁰¹ and R⁶⁰² are each independently hydrogen, or C₁-C₂₅ alkyl.
 7. A compound of formula

where Y, Y¹⁵, Y¹⁶ and Y¹⁷ are each independently of formula

where R¹, R², R⁶⁰¹ and R⁶⁰² are as defined in claim 1; p is 0, or 1, q is 0, or 1; A¹ and A² are each independently of formula

where a is 0, 1, 2, or 3, b is 0, 1, 2, or 3; c is 0, 1, 2, or 3; A³, A⁴, A⁵ and A^(5′) are each independently of formula —[Ar⁴]_(k′)—[Ar⁵]_(l)—[Ar⁶]_(r)—[Ar⁷]_(z)—, where k′ is 0, 1, 2, or 3; l is 0, 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1,2, or 3; R¹⁰ is hydrogen, halogen, cyano, C₁-C₂₅ alkyl, C₁-C₂₅ alkyl which is substituted one or more times by E″ and/or interrupted one or more times by D″,

COO—C₁-C₁₈ alkyl, C₄-C₁₈ cycloalkyl group, C₄-C₁₈ cycloalkyl group, which is substituted by G″, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₁-C₁₈ thioalkoxy, C₁-C₁₈ alkoxy, C₁-C₁₈ alkoxy which is substituted by E″ and/or interrupted by D″, C₇-C₂₅ aralkyl, C₇-C₂₅ aralkyl, which is substituted by G″, or a group of formulae IVa to IVm,

where R²² to R²⁶ and R²⁹ to R⁵⁸ each independently represent H, halogen, cyano, C₁-C₂₅ alkyl, C₁-C₂₅ alkyl which is substituted by E″ and/or interrupted by D″, C₆-C₂₄ aryl, C₆-C₂₄ aryl which is substituted by G″, C₂-C₂₀ heteroaryl, C₂-C₂₀ heteroaryl which is substituted by G″, a C₄-C₁₈ cycloalkyl group, a C₄-C₁₈ cycloalkyl group, which is substituted by G″, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, C₁-C₁₈ alkoxy, C₁-C₁₈ alkoxy which is substituted by E″ and/or interrupted by D″, C₇-C₂₅ aralkyl, or C₇-C₂₅ aralkyl, which is substituted by G″, R²⁷ and R²⁸ are each independently hydrogen, C₁-C₂₅ alkyl, halogen, cyano or C₇-C₂₅ aralkyl, or R²⁷ and R²⁸ together represent alkylene or alkenylene which optionally are both bonded via oxygen and/or sulfur to the thienyl residue and which optionally both have up to 25 carbon atoms, R⁵⁹ is hydrogen, C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; or C₁-C₂₅ alkyl, which optionally is interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅ arylalkyl, D″ is —CO—, —COO—, —S—, —O—, or NR^(112″)—, E″ is C₁-C₈thioalkoxy, C₁-C₈ alkoxy, CN, —NR^(112″)R^(113″), —CONR^(112″)R^(113″), or halogen, G″ is E″, or C₁-C₁₈ alkyl, and R^(112″) and R^(113″) are each independently H; C₆-C₁₈ aryl; C₆-C₁₈ aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—; R²¹⁴ and R²¹⁵ are each independently hydrogen, C₁-C₁₈ alkyl, C₆-C₂₄ aryl, C₂-C₂₀ heteroaryl, —CN or COOR²¹⁶; R²¹⁶ is C₁-C₂₅ alkyl, C₁-C₂₅ haloalkyl, C₇-C₂₅ arylalkyl, C₆-C₂₄ aryl or C₂-C₂₀ heteroaryl; R²¹⁸ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈ alkyl, or C₁-C₁₈ alkoxy; or C₁-C₂₅ alkyl, which optionally is interrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅ arylalkyl, Ar¹, Ar², Ar³ Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are each independently of each other a group of formula (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIg), (XIh), (XIi), (XIj), (XIk), (XIl), (XIm), (XIn), (XIo), (XIpa), (XIpb), (XIq), (XIr), (XIs), (XIt), (XIu), (XIv), (XIw), (XIx), (XIy), (XIz), (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIlj), (XIIk), (XIIl), (XIV), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr), (XVs), (XVt), (XVuc), or (XVu).
 8. The compound according to claim 7, which is a compound of formula A¹-Y-A³-Y¹⁵-A² (VIIIa), A¹-Y-A³-Y¹⁵-A⁴-Y¹⁶-A² (VIIIb), A-Y-A³-Y¹⁵-A⁴-Y¹⁶-A⁵-Y¹⁷-A² (VIIIc), A¹-A³-Y-A⁴-A² (IXa), A¹-A³-Y-A⁴-Y¹⁵-A⁵-A² (IXb), or A¹-A³-Y-A⁴-Y¹⁵-A⁵-Y¹⁷-A^(5′)-A² (IXc), wherein where Y, Y¹⁵, Y¹⁶ and Y¹⁷ are each independently of formula

where R¹ and R² are each independently of formula

where R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are each independently H, CN, F, CF₃, C₁-C₁₈ alkoxy; C₁-C₁₈ alkyl; or C₁-C₁₈ alkyl which is interrupted by —O—, or R¹ and R² together form a group

and R⁶⁰¹ and R⁶⁰² are each independently hydrogen, or C₁-C₂₅ alkyl, A³, A⁴, A⁵ and A^(5′) are each independently of formula

where R³, R^(3′), R⁴ and R^(4′) are each independently hydrogen, or C₁-C₂₅ alkyl; R⁸ and R^(8′) are each independently hydrogen, or C₁-C₂₅ alkyl; R¹¹⁴ is a C₁-C₃₈ alkyl group; R²⁰¹ is a C₁-C₃₈ alkyl group; and R²⁰² and R^(203′) are each independently hydrogen or C₁-C₂₅ alkyl.
 9. An organic semiconductor material, layer or component, comprising the polymer according to claim
 1. 10. An electronic device, comprising the polymer according to claim
 1. 11. The electronic device according to claim 10, which is an organic light emitting diode, an organic photovoltaic device, a photodiode, or an organic field effect transistor.
 12. A process for preparing an electronic device, the process comprising: applying a solution and/or dispersion of the polymer according to claim 1 in an organic solvent to a suitable substrate, and removing the solvent.
 13. A compound of formula

where A^(1′) and A^(2′) are each independently of formula

where X² and X^(2′) are each independently halogen, ZnX¹², —SnR²⁰⁷R²⁰⁸R²⁰⁹, where R²⁰⁷, R²⁰⁸ and R²⁰⁹ are each independently H or C₁-C₆ alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X¹² is a halogen atom; or —OS(O)₂CF₃, —OS(O)₂— aryl, —OS(O)₂CH₃, —B(OH)₂, —B(OY¹)₂,

—BF₄Na, or —BF₄K, where Y¹ is independently in each occurrence a C₁-C₁₀ alkyl group and Y² is independently in each occurrence a C₂-C₁₀ alkylene group, and Y¹³ and Y¹⁴ are each independently hydrogen, or a C₁-C₁₀ alkyl group, and a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴, A⁵ and A^(5′) are as defined in claim
 7. 14. A polymer, comprising a repeating unit of formula

where A^(1′) and A^(2′) are each independently of formula

where a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴, A⁵ and A^(5′) are as defined in claim
 7. 